Process for the preparation of azo dyestuffs having an aniline-type coupler by aminolysis of the appropriate ether group-containing compounds

ABSTRACT

An azo dyestuff of the formula ##STR1## wherein D=a diazo component, 
     R 1  and R 2  =alkyl or aralkyl, 
     R 3  =H, R or OR 1  and 
     R 4  =a hydrocarbon radical or acyl, 
     which are prepared in a simple manner by aminolysis with ammonia or an amine of the formula ##STR2## of an azo compound of the formula ##STR3## these dyestuffs dye polyester fibres in blue-green to green shades with good fastness to light.

The invention relates to a process for the preparation of non-ionic azo dyestuffs of the formula ##STR4## wherein D represents the radical of a diazo component which conains at least one non-ionic electron-withdrawing substituent,

R₁ and R₂ independently of one another denote hydrogen or an optionally substituted alkyl or aralkyl radical, or--together--denote an alkylene group,

R₃ denotes hydrogen, OR₁ or R₁ and

R₄ denotes hydrogen or an alkyl, aralkyl, aryl, hetaryl or acyl radical.

The compounds of the formula I are known in most cases and are useful disperse dyestuffs.

Suitable diazo components D are both aromatic and heteroaromatic radicals, in particular those of the benzene, naphthalene, thiophene, thiazole, thiazole, thiadaizole, benzothiazole, benzisothiazole and pyrazole series.

Suitable electron-withdrawing substituents are CF₃, alkylsulphonyl, arylazo, acyl, CN and, above all, NO₂.

Suitable acyl radicals are radicals of the formulae --COR₁, --COOR₁, --CONH₂, --CONHR₁, --CONR₁ R₂, --COH and --COR₃, R₃ denoting aryl or hetaryl.

Suitable alkyl radicals R₁ /R₂ are, for example, those with 1-6 C atoms which are optionally substituted by OH or C₁ -C₄ -alkoxy.

Suitable aryl radicals R₁ -R₃ and X, inter alia, are phenyl radicals, which can be substituted by CF₃, halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

Suitable aralkyl radicals are phenyl-C₁ -C₃ -alkyl radicals, which can be substituted in the phenyl radical as described above.

Suitable alkylene groups R₁ +R₂ are --(CH₂)_(n) (n=4-5).

Suitable halogen atoms are F and, above all, Br and Cl.

The compounds I are usually obtained by a process in which amines of the formula D--NH₂ are diazotized and the diazotization products are coupled with anilines of the formula ##STR5##

This process has the diasvantage, however, that the coupling components of the formula shown are frequently relatively difficult to obtain and/or the coupling itself does not proceed quantitatively, which results in low yields and an insufficient purity of the process products.

It has now been found that the compounds of the formula I are obtained in a more simple manner and in some cases in a better quality and yield by a process in which azo compounds of the formula ##STR6## wherein D, R₃ and R₄ have the abovementioned meaning and

R represents R₁,

are reacted with ammonia or amines of the formula ##STR7##

It must be regarded as decidedly surprising that this reaction proceeds so smoothly, since such exchange reactions usually only lead to satisfactory results if the --OR substituent in the para-position is very highly activated by nitro groups in the ortho-position (compare German Pat. No. A-2,528,866) or a quaternary diazo component D (compare German Pat. Nos. A-1,137,815 and 2,908,135), and is not--as in the present case--singly or doubly deactivated by the substituent --NHR₄ and, where appropriate, with R₃ ≠H.

It was also not to be excluded from the beginning that cleavage of the azo bridge takes place during aminolysis of the OR group (compare Chem. Abstr. 82, 124 931s (1975) and 89, 129 453s (1982)).

The process according to the invention can be carried out in water or organic solvents or in aqueous-organic media. The process is advantageously carried out with a stoichiometric excess of the amines III, which then at the same time assume the role of solvent. The aminolysis is in general carried out at 50°-150° C., preferably 80°-120° C., that is to say under relatively mild conditions.

The course of the reaction and the end of the reaction can easily be monitored or determined by thin layer chromatography.

Preferred azo compounds II which are to be employed are:

(1) Compounds of the formula ##STR8## wherein R₄ denotes hydrogen or an alkyl, aralkyl, aryl, hetaryl or acyl radical,

R'₁ denotes C₁ -C₄ -alkyl,

R'₂ denotes C₁ -C₄ -alkyl,

Y₁ denotes F, Cl, Br, I, CN or NO₂ and

Y₂ denotes Y₁ or CF₃, SO₂ R'₁, CO₂ R₁, COR'₁ or OR₁,

(2) and those of the formula ##STR9## wherein D' denotes the radical of a heterocyclic diazo component of the type mentioned above, in particular those of the formulae ##STR10## wherein T₁ =NO₂, CN or COOR₁,

T₂ =H or CH₃,

T₃ =NO₂, CN, COOR₁, COR₁, COR₃, SO₂ R₁, SO₂ R₃ or phenylazo,

T₂ +T₃ =--CH₂ CH₂ CH₂ CH₂ -- or --CH₂ CH₂ CH₂ --,

T₄ =H, CH₃ or phenyl,

T₅ =NO₂, COOR₁, CN or phenylazo,

T₆ =Br, NO₂ or CN,

T₇ =H, R₁, R₃ or SO₂ R₁ /R₃,

T₈ =Cl, Br, CN, phenyl or SR₁,

T₉ =Cl, Br, CF₃, SO₂ R₁ /R₃ or SR₁,

T₁₀ =R₁, R₃, Cl, Br or COOR₁,

T₁₁ =H or R₁,

T₁₂ =NO₂, CN, Cl, Br, COOR₁ and

T₁₃ =H, CN or R₁,

and wherein

R₁ /R₃ /R₄ have the abovementioned meaning,

it being possible for the rings labelled A and the phenylazo radical to be substituted by R₁, Cl, Br, NO₂, CN, COOR₁, SCN or SO₂ R₁.

The compounds of the formulae II, IV and V are known only in an individual case (compare German Patent Specification Nos. 643,058 and 744,215 and U.S. Pat. No. 2,870,137), but are in all cases readily accessible by methods which are known per se.

Compounds of the stated formulae from the benzisothiazole series are especially preferred.

Examples which may be mentioned of compounds of the formula III are: methylamine, ethylamine, chloroethylamine, hydroxyethylamine, butylamine, hexylamine, isopropylamine, 3-methyl-butanamine, allylamine, stearylamine, diethylamine, dipropylamine, dibutylamine, 2-ethyl-hexylamine, ditridecylamine, N-ethylisoprylamine, N-methylisobutylamine, N-methylstearylamine, 2-ethoxyethylamine, diallylamine, di-2-methoxyethylamine, 3-ethylaminopropionitrile, N-ethyl-butylamine, 3-methoxypropylamine, 3-ethoxy-propylamine, 3-butoxypropylamine, 3-(2-ethoxyhexoxy)-propylamine, diethanolamine, isopropanolamine, diisopropanolamine, 2-(2-amino-ethoxy)ethanol, 2-propylaminoethanol, 2-butylaminoethanol, cyclopropane-amine, cyclohexane-amine, N-ethyl-cyclohexane-amine, benzylamine, 2-phenylethylamine, 2-methoxyphenylethylamine, 4-methoxyphenylethylamine, 3,4-dimethoxyphenylethylamine, 4-hydroxyphenylethylamine, 2-diethylaminoethylamine, 3-dimethylaminopropylamine, N-methyl-1,3-propanediamine, diethylenetriamine, aniline, 4-methoxyaniline, 3-chloroaniline, 4-dimethylamino-aniline, 3,4-dimethoxyaniline, p-toluidine, 3-amino-acetanilide, 1-aminonaphthalene, pyrrolidine, piperidine, piperazine, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, 4-methylpiperidine, morpholine, 2-aminomethyl-furan, hexamethyleneimine, imidazole, butyl 3-butylamino-propionate, dimethyl 2-butylamino-ethanephosphate, 3-butylaminopropionitrile, 2-methylaminoethanesulphonic acid, 3-aminopropionic acid and 3-amino-tetramethylene sulphone.

Possible solvents for the aminolysis are: water, amines employed in excess and alcohols, such as methanol, ethanol, propanol, isopropanol, n- or iso-butanol, glycol, glycol ethers, such as 2-methoxy-ethanol, 2-ethoxyethanol, 2-isopropoxy-ethanol, 2-butoxyethanol, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and propylene glycol monoethyl ether, dioxane, esters, such as methyl glycol acetate and propylene glycol monomethyl ether-acetate, amides, such as formamide, dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone and tetramethylurea, nitriles, such as acetonitrile, 2-hydroxy-propionitrile and 2-methoxy-propionitrile, sulphones, such as dimethyl sulphone and tetramethylene sulphone, dimethylsulphoxide and (het)aromatic compounds, such as toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, pyridine, picoline or quinoline.

The solvents can also be employed as a mixture with one another.

In the examples which follow, "parts" denote parts by weight.

Dyestuffs of the formula ##STR11## wherein Z₁ =C₁ -C₄ -alkyl,

Z₂ =C₁ -C₄ -alkyl,

Z₃ =H, Z₄, ##STR12## --SO₂ --Z₄ or ##STR13## and Z₄ =C₁ -C₄ -alkyl,

are new and therefore the invention likewise relates to them.

They dye polyester fibres in blue-green to green shades with good fastness to light.

Particularly preferred dyestuffs are those of the formula (IV) wherein:

Z₁ =C₁ -C₂ -alkyl

Z₂ =CH₃, C₂ H₅ or n--C₄ H₉ and

Z₃ =COCH₃,

and mixtures of these dyestuffs which differ in respect of the definition of Z₂.

EXAMPLE 1

5.5 parts of the dyestuff of the formula ##STR14## (prepared according to German Reichspatent No. 744,215) are heated at 100° C. in a mixture of 50 parts of dimethylformamide and 10 parts of pyridine with 5 parts of 2-methoxyethylamine for 75 minutes. After the mixture has cooled to 80° C., 50 parts of methanol are added and the dyestuff formed, of the formula ##STR15## is filtered off, after cooling; yield: 5 parts. It dyes polyethylene terephthalate fibres in red-violet; shades and is characterized by a λ_(max) value of 560 nm at a molar extinction ε.sub.λmax of 40,800 [l/mol-cm], measured in dimethylformamide.

EXAMPLE 2

5.5 parts of the dyestuff of the formula ##STR16## (prepared by coupling diazotized 2-amino-5-nitro-benzonitrile to 3,4-dimethoxy-butyric acid anilide) are heated at 100° C. in 50 parts of N-methylpyrrolidone with the addition of 3 parts of p-anisidine for 20 hours, with stirring. After addition of 50 parts of methanol, 6 parts of the dyestuff of the formula ##STR17## are isolated, after cooling. It dyes polyester fibres in reddish-tinged blue shades which are fast to light and sublimation. λ_(max) : 600 nm; ε.sub.λmax 45,415 (dimethylformamide).

EXAMPLE 3

6.8 parts of the dyestuff of the formula ##STR18## (prepared from diazotized 2-bromo-4,6-dinitro-aniline and 3,4-dimethoxy-acetanilide) are heated at 100° C. in 50 parts of dimethylacetamide with 5 parts of ethyl-3,6,9-trioxadecylamine for 3 hours. After cooling, the dyestuff formed is precipitated with 100 parts of water. It probably has the following structure ##STR19## and dyes polyester in navy blue shades; λ_(max) : 608 nm, ε.sub.λmax : 34,420 (dimethylformamide).

EXAMPLE 4

67 parts of the dyestuff of the formula ##STR20## (prepared from diazotized 2,6-bromo-4-dinitro-aniline and N-[3,4-dimethoxyphenyl]-butanesulphonic acid amide) are warmed at 100° C. in 80 parts of dimethylformamide with 14 parts of zinc cyanide, 2 parts of copper(I) cyanide and 30 parts of 4-ethoxy-aniline. After cooling and addition of 200 parts of methanol, 52 parts of the reaction product of the formula ##STR21## are isolated. The dyestuff dyes polyester fibres in greenish-tinged blue shades with good fastness to light and sublimation.

λ_(max) 592 nm; ε.sub.λmax : 66,900 (dimethylformamide).

The dyestuffs of the formula ##STR22## according to the following Table 1 are obtained in an analogous manner starting from corresponding azo compounds of the formula II (wherein R=CH₃ or CH(CH₃)₂):

    TABLE 1       Example            λmax (nm) No. X.sub.1 X.sub.2 X.sub.3 X.sub.4      X.sub.5 R.sub.3 R.sub.1 R.sub.2 R.sub.4 Solvent Temp. (°C.) in      DMF  5 Cl H NO.sub.2 H H CH(CH.sub.3).sub.2 CH.sub.2CH.sub.2 CH.sub.2      CH.sub.2 COCH.sub.3 DMF/Pyridine 25 588 6 Cl H NO.sub.2 H H CH(CH.sub.3).      sub.2 H (CH.sub.2).sub.3OCH.sub.3  COCH.sub.3 DMF/Pyridine 80 564 7 Cl H      NO.sub.2 H H CH(CH.sub.3).sub.2 H C.sub.4       H.sub.9 COCH.sub.3 DMF/Pyridine 100 568 8 Br H NO.sub.2 H H OCH.sub.3 H C      .sub.6 H.sub.11 COCH.sub.3 DMF/Pyridine 100 565 9 NO.sub.2 H NO.sub.2 H      H OCH.sub.3  CH.sub.2CH.sub.2CH.sub.2CH.sub.2 COC.sub.2 H.sub.5 DMF 80      607 10 NO.sub.2 H NO.sub.2 H H OCH.sub.3 CH.sub.3 CH.sub.2C.sub.6      H.sub.5  COC.sub.2 H.sub.4OCH.sub.3 DMF 80 574 11 NO.sub.2 H NO.sub.2 H      Br OCH.sub.3 C.sub.2 H.sub.5 C.sub.3       H.sub.7 SO.sub.2CH.sub.3 NMethylpyrrolidine 25 598 12 NO.sub.2 H      NO.sub.2 H Br OCH.sub.3 C.sub.2 H.sub.5 C.sub.4 H.sub.9 SO.sub.2C.sub.4      H.sub.9 NMethylpyrrolidine 25 600 13 NO.sub.2 H NO.sub.2 H Br OCH.sub.3      C.sub.2 H.sub.5 C.sub.3 H.sub.7 SO.sub.2 C.sub.6       H.sub.5 NMethylpyrrolidine 25 582 14 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 (      CH.sub.2).sub.6  COC.sub.3 H.sub.7 NMethylpyrrolidine 25 618 15 NO.sub.2      H NO.sub.2 H Br OCH.sub.3 CH.sub.3 C.sub.18       H.sub.37 COCH.sub.3 Dimethylacetamide 80 610 16 NO.sub.2 H NO.sub.2 H      Br OCH.sub.3 C.sub.4 H.sub.9 C.sub.2 H.sub.4       P(OCH.sub.3).sub.2 COCH.sub.3 DMF/Pyridine 100 17 NO.sub.2 H NO.sub.2 H      Br OCH.sub.3 C.sub.4 H.sub.9 C.sub.2 H.sub.4 COOC(CH.sub.3).sub.3      COCH.sub.3 DMF/Pyridine 100 18 NO.sub.2 H NO.sub.2 H Br OCH.sub.3      C.sub.4 H.sub.17 C.sub.8 H.sub.17 COC.sub.3 H.sub.7 DMF/Pyridine 80 618      19 CN H NO.sub.2 H H OCH.sub.3 H (CH.sub.2).sub.3 OC.sub.3 H.sub.7      COC.sub.2 H.sub.4 OC.sub.2 H.sub.5 DMF 80 590 20 CN H NO.sub.2 H H      OCH.sub.3 (CH.sub.2).sub.6  COC.sub.2 H.sub.4 OC.sub.2 H.sub.5 DMF 80      602 21 CN H NO.sub.2 H Br OCH.sub.3 H C.sub.4 H.sub.9 COC.sub.2 H.sub.4      OCH.sub.3 DMF 25 628 22 CN H NO.sub.2 H Br OCH.sub.3 CH.sub.3 CH.sub.2      C.sub.6 H.sub.5 COC.sub.2 H.sub.4 OCH.sub.3 DMF 60 628  23 CN H NO.sub.2      H Br OCH.sub.3 H       ##STR23##       COC.sub.2 H.sub.4 OCH.sub.3 DMF 25 610  24 CN H NO.sub.2 H Br OCH.sub.3      H C.sub.2 H.sub.4 OCH.sub.3 COC.sub.2 H.sub.4 OCH.sub.3 DMF 60 618  25      CN H NO.sub.2 H Br OCH.sub.3 H       ##STR24##       COCH.sub.3 DMF/Pyridine 140 629  26 CN H NO.sub.2 H Br OCH.sub.3      (CH.sub.2).sub.6 COCH.sub.3 DMF/Pyridine 25 643 27 Br H NO.sub.2 H      NO.sub.2 H CH.sub.3 C.sub.2 H.sub.5 COCH.sub.3 DMF/Pyridine 25 563 28 CN      H NO.sub.2 H NO.sub.2 H C.sub.2 H.sub.5 C.sub.3 H.sub.7 COC.sub.3      H.sub.7 DMF/Pyridine 25 604 29 CN H NO.sub.2 H NO.sub.2 OCH.sub.3      C.sub.4 H.sub.9 C.sub.4 H.sub.9 COCH.sub.3 DMF/Pyridine 25 642 30 CN H      NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.4N(CH.sub.3).sub.2       (p) SO.sub.2C.sub.4 H.sub.9 DMF 40 616 31 CN H NO.sub.2 H CN OCH.sub.3      H C.sub.6 H.sub.4NHCOCH.sub.3 (m) SO.sub.2C.sub.4 H.sub.9 DMF 60 584 32      CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.4Cl(p) SO.sub.2C.sub.4      H.sub.9 DMF 85 586 33 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6       H.sub.4CH.sub.3 (o) SO.sub.2C.sub.4 H.sub.9 DMF 85 576 34 CN H NO.sub.2      H CN OCH.sub.3 H C.sub.10 H.sub.7 (α) SO.sub.2C.sub.4 H.sub.9 DMF      80 584 35 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.5 SO.sub.2C.sub.4      H.sub.9 DMF 60 584 36 CN H NO.sub.2 H CN OCH.sub.3 C.sub.2 H.sub.4      OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 SO.sub.2 CH.sub.3 DMF 45 636 37 CN H      NO.sub.2 H CN OCH.sub.3  C.sub.2 H.sub.5 C.sub.3 H.sub.7 SO.sub.2      C.sub.6 H.sub.5 DMF 25 640 38 CN H NO.sub.2 H CN OCH.sub.3 C.sub.2      H.sub.5 C.sub.4 H.sub.9 COC.sub.6 H.sub.4CH.sub.3(m) DMF 50 646 39 CN H      NO.sub.2 H CN OCH.sub.3 C.sub.4 H.sub.9 C.sub.4 H.sub.9 COOC.sub.2      H.sub.5 NMethylpyrrolidone 25 640 40 CN H NO.sub.2 H CN OCH.sub.3      C.sub.2 H.sub.5 C.sub.3 H.sub.7 COC.sub.3 H.sub.7 NMethylpyrrolidone 80      640

EXAMPLE 41 ##STR25## (prepared from diazotized 3-amino-5-nitro-benzisothiazole (2.1) N-(3,4-dimethoxyphenyl)-propionic acid amide) are heated at 80° C. in 100 ml of dimethylformamide with 10 parts of N-ethyl-propylamine for 2 hours, with stirring. After addition of 200 ml of methanol and cooling, 10 parts of the dyestuff of the formula ##STR26## are isolated. It dyes polyester materials in bluish-tinged green shades with good fastness to light; λ_(max) : 665 nm (dimethylformamide).

The dyestuffs of the formula ##STR27## listed in Table 2 were obtained from the dyestuffs ##STR28##

    TABLE 2       Example       Temp. in λ.sub.max (DMF) No. D R.sub.3 R.sub.1      R.sub.2 R.sub.4 Solvent (°C.) in nm                 42       OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 COCH.sub.3 NMethylpyrrolidone      50 668       43      ##STR29##       OCH.sub.3 CH.sub.3 C.sub.2 H.sub.4 OH COCH.sub.3 NMethylpyrrolidone 80      662       44      ##STR30##       OCH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.7 COC.sub.3       H.sub.7 NMethylpyrrolidone 80 669       45      ##STR31##       OCH.sub.3 C.sub.4 H.sub.9 C.sub.4 H.sub.9 COC.sub.3       H.sub.7 NMethylpyrrolidone 80 672       46      ##STR32##       OCH.sub.3 CH.sub.3 C.sub.18 H.sub.37 COCH.sub.3 Dimethylformamide 80      666       47      ##STR33##       OCH.sub.3 C.sub.2 H.sub.4 OH C.sub.2 H.sub.4       OH COCH.sub.3 Dimethylformamide  100 668       48      ##STR34##       OCH.sub.3 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 COCH.sub.3 Dimethylformamide      90 628       49      ##STR35##       OCH.sub.3 (CH.sub.2).sub.4 OC.sub.2       H.sub.4 COCH.sub.3 Dimethylformamide 25 680       50      ##STR36##       OCH.sub.3 H (CH.sub.2).sub.3N(CH.sub.3).sub.2 COCH.sub.3 Dimethylformami      de 80 656       51      ##STR37##       OCH.sub.3 H C.sub.2 H.sub.4 OCH.sub.3 COC.sub.2       H.sub.5 Dimethylformamide 70 649       52      ##STR38##       OCH.sub.3 H C.sub.4 H.sub.9 COC.sub.2 H.sub.5 Dimethylsulphoxide 80 654       53      ##STR39##       OCH.sub. 3 H (C.sub.2 H.sub.4 O).sub.4       CH.sub.3 COCH.sub.3 Dimethylformamide 80 652       54      ##STR40##       OCH.sub.3 H C(CH.sub.3).sub.3 COCH.sub.3 Dimethylformamide 90 646  55       ##STR41##       OCH.sub.3 H       ##STR42##       COCH.sub.3 Dimethylformamide 80 646       56      ##STR43##       OCH.sub.3 H (CH.sub.2).sub.3OC.sub.4 H.sub.9 COCH.sub.3 Water 80 654      57       ##STR44##       OCH.sub.3 H (CH.sub.2).sub.3OCH.sub.3 COCH.sub.3 Dimethylformamide 60      652       58      ##STR45##       OCH.sub.3 H (CH.sub.2).sub.3OC.sub.2       H.sub.5 COCH.sub.3 Dimethylformamide 60 657       59      ##STR46##       OCH.sub.3 H (CH.sub.2).sub.3OCH(CH.sub.3).sub.2 COCH.sub.3 Water 80 654       60      ##STR47##       OCH(CH.sub.3).sub.2 H (CH.sub.2).sub.3 COOH COC.sub.2 H.sub.5 DMF 80      650 (i)       61      ##STR48##       OCH(CH.sub.3).sub.2 H C.sub.2 H.sub.4SO.sub.3 H COC.sub.2 H.sub.5      NMethylpyrrolidone 80 668       62      ##STR49##       OCH.sub.3 CH.sub.3 C.sub.2 H.sub.4SO.sub.3 H CONH.sub.2 DMF 80  63       ##STR50##       OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.3 H.sub.7 SO.sub.2 C.sub.4      H.sub.9 Tetramethylenesulphone 80 764 (i)       64      ##STR51##       OCH.sub.3 CH.sub.2CH.sub.2 CH.sub.2CH.sub.2 SO.sub.2 C.sub.6 H.sub.5      Tetramethylsulphone 60 758       65      ##STR52##       OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 SO.sub.2 C.sub.4 H.sub.9 DMF      80 764       66      ##STR53##       OCH(CH.sub.3).sub.2 (CH.sub.2).sub.4  COCH.sub.3 DMF 25 688  67       ##STR54##       OCH(CH.sub.3).sub.2 CH.sub.3 C.sub.1       8H.sub.37 COCH.sub.3 Dimethylformamide 90 668       68      ##STR55##       OCH(CH.sub.3).sub.2 H C.sub.16 H.sub.33 COC.sub.3       H.sub.7 Dimethylformamide 80 661       69      ##STR56##       OCH(CH.sub.3).sub.2 H       ##STR57##       COC.sub.3 H.sub.7 Dimethylformamide 80 660       70      ##STR58##       OCH.sub.3 H C.sub.6 H.sub.5 COCH.sub.3 Dimethylformamide  100 662  71       ##STR59##       OCH.sub.3 H C.sub.6 H.sub.4OCH.sub.3 (p) COCH.sub.3 Dimethylformamide      110 674       72      ##STR60##       OCH.sub.3 H C.sub.6 H.sub.3 (OCH.sub.3).sub.2       (3,4) COCH.sub.3 Dimethylformamide  110 680       73      ##STR61##       OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COC.sub.2 H.sub.5 Dimethylformamide      50       74      ##STR62##       OCH.sub.3 C2H.sub.5 C.sub.2 H.sub.5 SO.sub.2 C.sub.4       H.sub.9 Dimethylformamide 80       75      ##STR63##       OCH.sub.3 C2H.sub.5 C.sub.2 H.sub.5 CONH.sub.2 Dimethylformamide 80 671       76      ##STR64##       OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COC.sub.4       H.sub.9 NMethylpyrrolidone 80 625 (i)       77      ##STR65##       OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COCH.sub.3 NMethylpyrrolidone 30      78       ##STR66##       OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COCH.sub.3 Dimethylformamide 80 608      nm (i)

EXAMPLE 79

258.9 parts of the dyestuff of the formula ##STR67## (prepared according to German Reichspatent No. 744,215) are heated at 100° C. in a solution of 22.9 parts of 3-methoxypropylamine, 26.5 parts of 3-ethoxypropylamine and 33.7 parts of n-butoxypropylamine in 600 parts of dimethylformamide for 75 minutes. After cooling to 80° C., 50 parts of methanol are added and the dyestuff formed, of the formula ##STR68## is filtered off, after cooling. Yield: 215.3 parts.

The dyestuff is distinguished by a good affinity for polyethylene terephthalate fibres, which are dyed in a green colour shade. 

I claim:
 1. A process for the preparation of a non-ionic azo dyestuff of the formula ##STR69## wherein D represents the radical of a diazo component which contains at least one non-ionic electron-withdrawing substituent selected from the group consisting of CF₃, alkylsulphonyl, arylazo, acyl, CN and, NO₂,R₁ and R₂ independently of one another denote hydrogen, unsubstituted alkyl or alkyl substituted by HO or C₁ -C₄ -alkoxy, unsubstituted aralkyl or aralkyl substituted in the aryl portion by OF₃, halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, or R₁ and R₂ taken together denote a C₄ -C₅ -alkylene group, R₃ denotes hydrogen, OR₁ or R₁ and R₄ denotes hydrogen, alkyl, aralkyl, aryl, or acyl,wherein an azo compound of the formula ##STR70## in which R represents R₁ is reacted with ammonia or an amine of the formula ##STR71## wherein said reaction is carried out in water, an organic solvent or in aqueous-organic media at a temperature of from 50°-150° C.
 2. A process according to claim 1, wherein a compound of the formula ##STR72## wherein R₄ denotes hydrogen, alkyl, aralkyl, aryl, hetaryl or acyl,R'₁ denotes C₁ -C₄ -alkyl, R'₂ denotes C₁ -C₄ -alkyl, Y₁ denotes F, Cl, Br, I, CN, NO₂ or OR'₁ and Y₂ denotes Y₁ or CF₃, SO₂ R'₁, CO₂ R₁ or COR'₁, is reacted with ammonia or the amine.
 3. A process according to claim 1, wherein a compound of the formula ##STR73## wherein D' denotes a hetaryl of the formula ##STR74## wherein T₁ =NO₂, CN or COOR₁,T₂ =H or CH₃, T₃ =NO₂, CN, COOR₁, COR₁, COR₃, SO₂ R₁, SO₂ R₃ or phenylazo, T₂ +T₃ =--CH₂ CH₂ CH₂ CH₂ -- or --CH₂ CH₂ CH₂ --, T₄ =H, CH₃ or phenyl, T₅ =NO₂, COOR₁, CN or phenylazo, T₆ =Br, NO₂ or CN, T₇ =H, R₁, R₃ or SO₂ R₁ /R₃, T₈ =Cl, Br, CN, phenyl or SR₁, T₉ =Cl, Br, CF₃, SO₂ R₁ /R₃ or SR₁, T₁₀ =R₁, R₃, Cl, Br or COOR₁, T₁₁ =H or R₁, T₁₂ =NO₂, CN, Cl, Br, COOR₁ and T₁₃ =H, CN or R₁,the rings labelled A and the phenyl-azo are unsubstituted or substituted by R₁, Cl, Br, NO₂, CN, COOR₁, SCN or SO₂ R₁, is reacted with ammonia or the amine.
 4. A process according to claim 1, wherein the reaction is carried out at 50°-150° C.
 5. A dyestuffs of the formula ##STR75## wherein Z₁ =C₁ -C₄ -alkyl,Z₂ =C₁ -C₄ -alkyl, Z₃ =H, Z₄, --SO₂ --Z₄ or ##STR76## and Z₄ =C₁ -C₄ -alkyl.
 6. Dyestuff according to claim 5, whereinZ₁ =C₁ -C₂ -alkyl, and Z₂ =CH₃, C₂ H₅ or n-C₄ H₉. 